The PPh3-Substituted Hydroxycyclopentadienyl Ruthenium Hydride [2,5-Ph2-3,4-Tol2(η5-C4COH)]Ru(CO)(PPh3)H Is a More Efficient Catalyst for Hydrogenation of Aldehydes

2006 ◽  
Vol 25 (5) ◽  
pp. 1230-1235 ◽  
Author(s):  
Charles P. Casey ◽  
Neil A. Strotman ◽  
Sharon E. Beetner ◽  
Jeffrey B. Johnson ◽  
David C. Priebe ◽  
...  
Keyword(s):  
Efficient Catalyst ◽  
Ruthenium Hydride ◽  
Hydroxycyclopentadienyl Ruthenium Hydride

scholarly journals The PPh3-Substituted Hydroxycyclopentadienyl Ruthenium Hydride [2,5-Ph2-3,4-Tol2(η5-C4COH)]Ru(CO)(PPh3)H is a More Efficient Catalyst for Hydrogenation of Aldehydes.

2008 ◽  
Vol 27 (2) ◽  
pp. 304-304
Author(s):  
Charles P. Casey ◽  
Neil A. Strotman ◽  
Sharon E. Beetner ◽  
Jeffrey B. Johnson ◽  
David C. Priebe ◽  
...  
Keyword(s):  
Efficient Catalyst ◽  
Ruthenium Hydride ◽  
Hydroxycyclopentadienyl Ruthenium Hydride

Kinetic isotope effect evidence for the concerted transfer of hydride and proton from hydroxycyclopentadienyl ruthenium hydride in solvents of different polarities and hydrogen bonding ability

2005 ◽  
Vol 83 (9) ◽  
pp. 1339-1346 ◽  
Author(s):  
Charles P Casey ◽  
Jeffrey B Johnson
Keyword(s):  
Hydrogen Bonding ◽  
Isotope Effect ◽  
Kinetic Isotope Effect ◽  
Methylene Chloride ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Additional Energy ◽  
Ruthenium Hydride ◽  
Kinetic Isotope ◽  
Hydroxycyclopentadienyl Ruthenium Hydride

The tolyl analogue of Shvo's hydroxycyclopentadienyl ruthenium hydride (4) efficiently transfers a hydride and proton to benzaldehyde or acetophenone to produce an alcohol. This reduction can be performed in toluene, methylene chloride, and THF. Reduction of benzaldehyde in toluene and methylene chloride occurs approximately 300 times faster than in THF at 0 °C. Reduction of acetophenone occurs between 75 and 150 times slower than benzaldehyde at 0 °C in each respective solvent. Despite the differences in rate, mechanistic studies have provided evidence for a similar concerted transfer of acidic and hydridic hydrogens in each solvent. Addition of water to THF led to further rate decrease coupled with an increase in the OH/D kinetic isotope effect and a decrease in the RuH/D kinetic isotope effect. Addition of excess alcohol to toluene or methylene chloride results in the significant retardation of the rate of reduction. The slower rate in THF and in the presence of alcohol is attributed to the stabilization of the ground state of ruthenium hydride 4 by hydrogen bonding and the additional energy required to break these bonds prior to carbonyl reduction.Key words: ruthenium hydrogenation catalysis, hydrogenation mechanism, kinetic isotope effects, ligand–metal bifunctional catalysis.

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